Cationic rhodium bis(dioxaphosphorus heterocycle) complexes and their use in the branched product regioselective hydroformylation of olefins

ABSTRACT

Cationic rhodium bis(dioxaphosphorus heterocycle) complexes of the formula: ##STR1## in which R is preferably ##STR2## or (CH 2 ) 2-5 , Y . . . Y is any backbone chain of 2-5 atoms, and L and L&#39; are any stabilizing ligands, used in hydroformylation of olefins to obtain regioselectivity of branched aldehyde products. The formula of the catalyst may include substituents which do not interfere with the branched product regioselectivity of the catalyst as a whole. In the hydroformylation method the olefin is reacted with hydrogen and carbon monoxide in the presence of the catalyst at a temperature and pressure sufficient to permit the desired branched product regioselectivity.

FIELD OF THE INVENTION

The present invention pertains to novel cationic rhodium complexes ofbis(1,3,2-dioxaphosphorus heterocycle) ligands for use in maximizing theproduction of branched aldehydes in the hydroformylation of olefins.Selectivity for the branched aldehyde isomer is important in thesynthesis of many pharmaceutical agents. The particular regioselectivehydroformylation reaction catalyzed by the use of cationic rhodiumcomplexes of the present invention is selective for the α-substitutedaryl aldehydes in a maximal way and results in the formation of abranched isomer that is useful for the synthesis of pharmaceuticals suchas ibuprofen.

BACKGROUND OF THE INVENTION

In general, the hydroformylation reaction involves the addition ofcarbon monoxide and hydrogen to an olefin containing a substituentgroup. In this reaction, two isomers are formed in which one is linear,A, and the other is branched, B. ##STR3##

The history of the utility of hydroformylation reactions has focusedprincipally on the preparation of linear products for subsequent use inmaking surfactants and detergents; however, the branched product is alsovery important for use in preparing speciality chemicals orpharmaceutical chemicals.

Selectivity for the branched or the linear isomer is important inproducing a single, pure product, and selectivity can be obtained bymanipulating the structure of a catalyst for the reaction, which istypically based on rhodium or cobalt.

Through the selection of a single, pure product, a better and moreefficient route to the production of α-aryl aldehydes is obtained, andthese aldehydes are precursors to α-aryl carboxylic acids, such as thoseforming the base for ibuprofen and naproxen.

Regioselective rhodium catalyzed hydroformylation, as reported by Amer,I., et al, J. Amer. Chem. Soc., 112, 3675 (1990), involves as catalyst asimple zwitterionic π-arene complex of Rh(1,5-cyclooctadiene)⁺ and BF₄⁻. This process is conceptually simple and the selectively, which istypically up to 98% branched, is very good; however, the range ofsubstrates reported therein do not include β-substituents (as in thecase of β-methyl styrene).

Drent, E., UK patent appl. GB 2217318, discloses the use of a formulabased on aryl phosphite and neutral Rh(I) that provides modestselectivity when the olefin containing substituent is vinyl acetate.

Neibecker, B. et al, J. Org. Chem., 54, 5208 (1989), discloses the useof a system based on a specific phosphine ligand that gives only 80-95%selectivity for the branched isomer.

In the regioselective catalyzed system of Brown, J. M. et al,Tetrahedron, 42, 5105 (1988), reliance is based upon a large, veryflexible disaccharide backbone; however, the backbone ligand is not easyto make and it is useful for only a limited range of substrates.

A survey of reactions of simple rhodium carbonyl catalysts that, atcertain high pressures and temperatures, is very effective, i.e., up toa 98:2 ratio, is reported in Lazzaroni, R. et al, J. Mol. Cat., 50, 1(1969).

Other literature and patent references pertaining to selectivehydroformylation are as follows: Agency of Industrial Sciences andTechnology, JP 48099131; Tanaka, M. et al, Bull. Chem. Soc. Jpn., 47,1698 (1974); Fujimoto, M. et al., JP 52062233; Pittman, C. U. Jr. etal., J. Org. Chem., et al, 43, 4928 (1978); Lai, V., et al, J. Mol.Catal. 4, 401 (1978); Takeda, et al, JP 54024843; Tinker, Harold B., etal., U.S. Pat. No. 4,268,688; and Hayashi, T. et al, J. Mol. Catal. 13,323 (1981).

SUMMARY OF THE INVENTION

Accordingly, it is an object of the present invention to provide newrhodium-based catalysts for hydroformylation reactions in order toselect a single branched aldehyde product.

Another object of the present invention is to provide a general route toobtaining branched aldehydes in order to facilitate proficiency in thesynthesis of certain pharmaceutical agents or other specialitychemicals.

A further object of the present invention is to provide catalystsconsisting of cationic rhodium complexes containing abis(dioxaphosphorus heterocycle) ligand, and applying this metal-ligandsystem in a hydroformylation reaction to efficiently and selectivelyarrive at the corresponding branched aldehydic products of the olefin.

Yet another object of the present invention is to provide appropriatereaction conditions so that said ligands or complexes will catalyze theformation of only the branched isomers derived from vinyl arenes, suchas styrene or vinyl naphthalene.

A still further object of the present invention is to provide a catalystthat is effective with substrates such as β-methyl styrene in order toprovide a high selectivity for the product with the formyl group next tothe arene.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

It has been discovered that a novel structure of cationic rhodiumcomplexes containing 1,3,2-dioxaphosphorus heterocyclic groups haveexcellent selectivity for the branched product in hydroformylationreactions. The particular cationic rhodium complexes in accordance withthe present invention have the following structural formula: ##STR4##This structure includes as its major components a rhodium(I) center, two1,3,2-dioxaphosphorus heterocyclic groups connected by their phosphorusatoms to the rhodium, and a backbone group linking the two phosphorusatoms and the rhodium atom into another ring structure. For stability,the rhodium ion is also connected to a ligand structure.

The catalysts of the present invention are effective for branchedregioselectivity in hydroformylation reactions because the1,3,2-dioxaphosphorus heterocyclic groups essentially keep any catalystsubstituents away from the active site at which the rhodium interactswith the reaction substrate. It is known that a crowded, or stericallyhindered, catalyst will show a preference for linear regioselectivity inhydroformylation reactions. The concept in the structure of the catalystof the present invention is to tie back the moieties connected to thephosphorus atoms so as to leave the rhodium as uncrowded as possible.This is done by means of the heterocyclic groups of the presentinvention.

The heterocyclic groups are shown in the above formula to be closed byan R group. The R group may be any group which includes 2 to 5 carbonatoms directly within the 1,3,2-dioxaphosphorus heterocyclic group,which carbon atoms are optionally substituted by any moiety which willnot interfere with the branched product regioselectivity of the catalystas a whole. Preferred R groups will have no substituents, but ifsubstituents are present, the preferred substituents are those whichmake the oxygens of the dioxaphosphorus heterocyclic groups moreelectron-withdrawing as this will cause the phosphorus atoms to beelectron-deficient. The smallest dioxaphosphorus heterocyclic groups arepreferred as it has been shown that five-membered 1,3,2-dioxaphosphorusgroups give somewhat better selectivity under identical conditions thansix-membered groups. Among the groups which may be used as R include--C₆ H₄ -- or --(CR¹ R²)_(x) -- where x is 2-5, preferably 2 or 3, andR¹ and R², alike or different, may be hydrogen, lower alkyl, phenyl or acarboxylato ester, optionally substituted by any group which will notinterfere with the ability of the catalyst as a whole to be branchedproduct regioselective. On a lower alkyl group, such substituents may betrifluoro, cyano, carbonyl or any other group which makes the oxygensmore electron-withdrawing. On a phenyl group, such substituents mayinclude alkyl, alkoxy and amino, but will preferably include any groupwhich is electron-withdrawing, e.g., halogen, nitro, etc. With respectto the carboxylato moieties, the ester may be an alkyl or aryl group,again optionally substituted by an group which will not interfere withthe ability of the catalyst as a whole to be branched productregioselective.

The Y . . . Y backbone group is also not critical to the catalyticactivity of the catalyst as a whole. Any backbone should work wellunless it somehow causes the rhodium ion to become more crowded and,thus, affect the branched product regioselectivity of the catalyst as awhole. Examples of such backbones are --O(CH₂)_(y) O--, --(CH₂)_(y) --,--(C₆ H₄)--, and --O(o--C₆ H₄)O--, in which y is 2-5, preferably 2 or 3.It is also possible to use nonorganic backbones such as --O--Si--O--.Again, any backbone group which provides a chain of 2-7 atoms betweenthe phosphorus atoms and which does not interfere with the ability ofthe catalyst as a whole to be branched product regioselective can beused.

Whenever the term "which does not interfere with the ability of thecatalyst as a whole to be branched product regioselective" is usedthroughout the present specification and claims with respect to asubstituent, radical or other group, it is intended that suchsubstituent, radical or group does not cause the hydroformylationreaction of interest to lose its selectivity for the branched aldehydeproduct. If the branched and linear products are approximately equal orif there is more linear product than branched then the catalyst is notconsidered to be branched product regioselective. As the preferredproducts are substantially 100% branched product regioselective, thepreferred substituents, radicals or groups will not substantially affectthat 100% regioselectivity and will permit at least 75% regioselectivityunder pressure conditions which are commercially reasonable.

In order to determine whether a catalyst with any given substituent,radical or group falls within the definition, i.e., does not interferewith the ability of the catalyst as a whole to be branched productregioselective, one need only run routine tests, such as that detailedin Example 4 hereinbelow. Such a test does not require undueexperimentation. Indeed, the determination of whether any givensubstituent, radical or group falls within this definition would be amatter of routine experimentation.

To be stable, the rhodium cation must be coordinated with ligands L andL' so that the stabilized catalyst will have the structure: ##STR5##However, such ligands do not play a part in the activity of the catalystas they are removed in situ and the rhodium ion complexes directly withthe reaction substrate being catalyzed. Precatalysts, which may bestored and added to the reaction so as to form the active catalyst insitu, must have such stabilizing ligands. When the stabilizing ligandsare used, the ligands may be any olefin or they may be CO groups.Alternatively, the ligands may be a coordinating solvent, such astetrahydrofuran, acetonitrile, methylene chloride, chloroform, acetone,etc. The L and L' groups may be combined into a single diolefin, such as1,5-cyclooctadiene (COD), norbornadiene, or 1,5-hexadiene.

The catalyst of the present invention is itself cationic. It may beprepared with any anion such as BF₄ ⁻, PF₆ ⁻, ClO₄ ⁻, a halide, etc. Theparticular anion used is not part of the present invention per se.

The catalysts of the present invention may be synthesized by firstsynthesizing the diphosphorus ligands and then reacting with a rhodiumcompound. Diphosphorus ligands containing 1,3,2-dioxaphosphorusheterocyclic groups are made by the condensation of a diol with PCl₃followed by linking with a backbone diol such as 1,3-propane diol orcatechol. Diols such as diisopropyltartrate, diethyltartrate andR,R-dihydrobenzoin react readily with PCl₃ in the presence of a base togive a chlorodioxaphosphorus heterocycle as a single stereoisomer asfollows: ##STR6## where Py is pyridine (but may be any other base), R¹and R², alike or different, are trifluoro, cyano, carbonyl or any othergroup which makes the oxygens of the dioxaphosphorus heterocycle moreelectron-withdrawing, and x is 2-5. When the diol starting material is atartrate, the diol formula has x being 2, the R¹ groups being hydrogenand the R² groups being --COOR³ where R³ is an alkyl or aryl group. Whenthe diol starting material is dihydrobenzoin, the diol formula x being2, R¹ being hydrogen and R² being phenyl. Whenever x is 2, the1,3,2-dioxaphosphorus heterocyclic compound produced is adioxaphospholane. Alternatively, the starting diol may be HO--(o--C₆H₄)--OH which is optionally substituted with one or more substituentshaving the same definition as R¹ and R².

In the case of the tartrate esters, the product is purified bydistillation in vacuo while the diphenyl derivative is obtained pureafter crystallization from ether. All three compounds are obtained inanalytically pure form in fair to good yield (46-93%), and while thesecompounds are sensitive to protic solvents, they are indefinitely stableat ambient temperatures under dry nitrogen.

The formation of the bis-phosphorus ligand may be performed with anyother diol in the presence of a base in accordance with the followingequation: ##STR7## where x, R¹ and R² are as described above, z is 2 to5, and R⁴ and R⁵ are any substituents which do not interfere with theability of the final catalyst to be branched product regioselective. R⁴and R⁵ are preferably both H and z is preferably 3. Reactions withaliphatic 1,2-diols such as ethylene glycol and pinacol are complicatedby the decomposition products which appear to involve an equilibriummixture of heterocyclic rings. Much better results are obtained with1,3-propanediol which affords good yields (71-90%) of the desireddiphosphorus products as oils. These oils can be purified tospectroscopic and analytical purity from ether. The NMR spectra of thesecomplexes are essentially the same as their acyclic analogues (shifts inthe ³¹ P NMR spectrum occur in a ca 0.145 ppm). They are thermallysensitive but can be stored at low temperature and handled for shortperiods at ambient temperatures.

Alternatively, a bis(dichlorophosphino)alkane can be reacted directlywith a diol to form the bis-dioxaphosphorus heterocycle auxiliarydirectly, as follows: ##STR8## where x is 2-5, y is 2-5 and R¹ and R²are as defined above.

Once the bis(1,3,2-dioxaphosphorus heterocycle) compounds are obtainedthey can readily form cationic rhodium precatalysts by reaction with aRh(I) rhodium compound such as Rh(I)⁺ L_(n) ⁻ or Rh(I)⁺ L_(n) X⁻. In thefirst instance L is an anionic coordinating ligand such as CO₂ Cl or acoordinating solvent such as tetrahydrofuran, acetonitrile, methylenechloride, chloroform, acetone, etc. In the second instance L is aneutral ligand such as an olefin or carbon monoxide. The neutral ligandmay be a cyclic group such as 1,5-cyclooctadiene (1,5-COD). n may be anynumber above 0 as long as the ligand is complexed with the rhodiumcation. The anion X⁻ may be any non-coordinating anion such as BF₄ ⁻,PF₆ ⁻, ClO₄ ⁻, a halide, etc. A preferred rhodium compound for making astable rhodium precatalyst is bis(1,5-cyclooctadiene) rhodiumtetrafluoroborate. This compound gives a good yield of analytically andspectroscopically pure complex salts.

EXAMPLE 1 Synthesis of 2-chloro-1,3,2-dioxaphospholanes

Phosphorus trichloride (3.2 g. 23 mmol) was dissolved in 60 ml oftetrahydrofuran (THF). A solution of R,R-dihydrobenzoin (5.00g. 23.4mmol) and anhydrous pyridine (4 ml, 51 mmol) in 60 ml THF was addeddropwise while the reaction flask was cooled in an ice water bath. Theresulting white suspension was stirred overnight at room temperature andfiltered. The product was isolated as spectroscopically pure colorlesscrystals (5.1 g 80%) after crystallization from diethyl ether at -78° C.

The tartrate ester derivatives were synthesized by addition of the PCl₃solution to the diol/pyridine solution, and superior yields wereobtained if the reaction was left to stir for several days. The clear,colorless filtrate was concentrated in vacuo and the crude productpurified by vacuum (ca. 10⁻³ Torr) distillation. Typical yields ofpurified products: from diethyltartrate were 93% (b.p., 93-95° C., 10-3Torr); and from diisopropyltartrate: 46% (b.p., 108-110° C.)

EXAMPLE 2 Synthesis of propane-bridged bis(dioxaphospholane)s

The chlorodioxaphospholane (3.00 g. 11 mmol) was dissolved in 20 ml THF.This solution was immersed in ice water and, with stirring, a solutionof 1,3-propanediol (0.41 g. 5.4 nmol) and anhydrous pyridine (1 ml.0.013 mol) in 15 ml THF was added dropwise over a period of 30 minutes.The mixture (which turns into a white suspension), was stirred for anadditional 3 hours and then filtered. The solvent was removed in vacuoand the product purified by extraction with ether and then filtered andconcentrated to give a colorless, spectroscopically pure oil (2.8 g90%). Typical yields of purified products from diethyltartrate are 77%;and from diisopropyltartrate: 71%.

EXAMPLE 3 Synthesis of (1,5-cyclooctadiene)bis(dioxaphospholane)rhodium(I) tetrafluoroborates

The bis(dioxaphospholane) (0.69g, 0.12 mmol) was dissolved in 5 mlmethylene chloride and added, via cannula, to a solution ofbis(1,5-cyclooctadiene)rhodium(I)tetrafluoroborate (0.50g, 1.23 mmol) in10 ml CH₂ Cl₂. The bright orange solution was concentrated in vacuo andthe residue was extracted with chloroform. The product was precipitatedfrom solution by the addition of Et₂ O (0.88 g 83%). Typical yields ofpurified products from diethyltartrate are 54%; and fromdiisopropyltartrate: 55%.

EXAMPLE 4 Hydroformylation reactions

A hydroformylation reaction was performed by loading substrate andcatalyst into a bomb in an inert atmosphere and then pressurizing to theappropriate initial pressure with 1:1 CO:H₂. The reaction was thenheated externally in an oil bath at 70° C. and then stopped after 24hours, and the vessel was then vented and opened to the air. Reactionproducts were determined by an examination of the reaction mixture by ¹H NMR after removal of most of the solvent by a stream of nitrogen or ina vacuum. Quantitative amounts of the linear and branched isomer weredetermined by comparison of the integrals of the signal for the linearisomer with the nearest ¹³ C satellite of the branched isomer. Wherecomplete regioselectivity is obtained, as in equation 2, this means thatthe ¹³ C satellites of the branched isomer are clearly visible while asignal for the linear isomer is not. This corresponds to at least a200:1 ratio of branched to linear isomer.

In this example the substrate was styrene and the catalyst was: ##STR9##When the reaction was performed at 250 psi, the product contained 85% ofthe branched product: PhCH(CHO)CH₃ and 15% of the linear product: PhCH₂CH₂ CHO. When repeated at 700 psi, complete selectivity for theisoaldehyde was obtained.

EXAMPLE 5

The hydroformylation reaction of Example 4 was repeated using vinylnaphthalene as the substrate. At 700 psi the selectivity was 98% for thebranched aldehydic product.

EXAMPLE 6

The hydroformylation reaction of Example 4 was repeated using vinylacetate as the substrate. At 700 psi the selectivity was 100% for thebranched aldehydic product.

EXAMPLE 7

The hydroformylation reaction of Example 4 was repeated using β-methylstyrene as the substrate. At 1450 psi 94% selectivity for the α-aldehydeis obtained. Thus, even with disubstituted olefins selectivity for theα-aldehyde product, while not 100%, is far superior to any prior artliterature reports.

In principle, the versatility of the formyl group created in thehydroformylation indicates that the catalyst of the present inventioncan be useful in countless applications. However, two problems can beeasily resolved through the use of the catalyst of the present inventionunder the conditions described. Namely, the simple production of α-arylaldehyde and the synthesis of chiral precursors for heterocyclesynthesis.

The α-aryl aldehydes are important precursors to α-aryl carboxylic acidsthat are the basis for a family of important biologically active agentssold over-the-counter, as, for example, the drug ibuprofen and theproprietary drug naproxen. Hydroformylation of an aryl olefin is anextremely attractive route to the aldehyde, which can be convenientlyoxidized to the acid, and the catalyst of the present invention can be amethod of choice for α-aryl aldehyde synthesis because the selectivityis so much higher than that in other systems.

In the synthesis of chiral precursors for heterocycle synthesis,aldehydes are also effective reagents relevant to pharmaceuticaldevelopment, especially when the α-carbon is branched, and the scope ofthe applications envisioned can, for example, be described in referenceto the following two recent reports:

1) Danishefsky and coworkers have developed the Lewis-acid catalyzedcondensation (LACDAC) of activated dienes and aldehydes as a route tofuran synthesis and, by elaboration of the furan, to a myriad of naturalproducts (cf. Danishefsky, S. Chemtracts, 1989, 2, 273). The reaction iscapable of generating new stereocenters with excellent selectivity ifthe aldehyde is branched at the α-position; and

2) A second application relies on methodology developed by Trost (cf.Trost, B. M. Angew. Chem., Int. Ed., Engl., 25, 1, (1988)) and Tsuju(cf. Shimuzu, I., et al Tetrahed. Lett., 25, 5183 (1984)) for palladiumcatalyzed formation of five-membered rings. Trost has shown that, withaldehydes, this constitutes a general route to substituted methylenefurans (cf. Trost, B. M. et al., J. Amer. Chem. Soc., 112, 408 (1990))Trost, B. M. et al., J. Amer. Chem. Soc.. 11, 5902 (1989)); Trost, B. M.et al., J. Amer. Chem. Soc.. 107, 8277 (1985)).

As to the item 1) above, the method of the present invention may be usedto greatly increase the number and complexity of substrates suitable forthe Lewis-acid catalyzed condensation of activated dienes and aldehydes.In connection with item 2) above, the method of the present inventioncan provide chiral aldehydes that induce excellent stereo-selectivity inthe reaction, and the products formed can be elaborated into naturalproducts and prodrugs.

While the invention has been described with specific reference to theuse of the cationic rhodium bis 1,3,2-dioxaphosphorus complexes forhydroformylation of olefins to branched aldehydes, it is to beunderstood that said examples are for purposes of illustration only andare not to be construed as limitations upon either the use of saidcatalysts or the processes specifically described using said catalysts,and that the catalyst complexes as well as the processes of using thesame can be applicable to any rhodium catalyzed hydroformylationreaction where regioselectivity is sought for the branched aldehydicproduct and in the synthesis of chiral precursors for heterocyclesynthesis, without departing from the spirit and scope of the invention,which is defined in the appended claims.

What is claimed is:
 1. A catalyst useful in the branched productregioselective hydroformylation of olefins, having the formula:##STR10## wherein R is any group which includes 2-5 carbon atomsdirectly within the 1,3,2-dioxaphosphorus heterocyclic group and whichdoes not interfere with the branched product regioselectivity of thecatalyst as a whole, and Y . . . Y is [--O(CH₂)₂ O--] --O(CH₂)_(y) O--,[--(CH₂)_(y) --] --(CR⁴ R⁵)_(y) --, --(C₆ H₄)--, --O(o--C₆ H₄)O-- or--O--Si--O--, in which y is 2-5, [or --O(CR⁴ R⁵)_(z) O-- where z is 3-5]and R⁴ and R⁵ are hydrogen or any substituent which does not interferewith the ability of the final catalyst to be branched productregioselective, said catalyst being stabilized by coordination with oneor more appropriate ligands.
 2. A catalyst in accordance with claim 1,wherein R is --(CR¹ R²)_(x) -- in which x is 2-5, R¹ and R², alike ordifferent, are hydrogen or any group which will not interfere with theability of the catalyst as a whole to be branched productregioselective, or a phenyl group connected at ortho carbon atoms to theoxygen atoms of the dioxaphosphorus heterocycle, said phenyl group beingunsubstituted or substituted by a substituent which will not interferewith the ability of the catalyst as a whole to be branched productregioselective.
 3. A catalyst in accordance with claim 2, wherein x is2.
 4. A catalyst in accordance with claim 2, wherein R¹ and R², alike ordifferent, are hydrogen, lower alkyl, phenyl or a carboxylato ester,wherein the alkyl, phenyl or carboxylato ester groups are unsubstitutedor substituted by any group which will not interfere with the ability ofthe catalyst as a whole to be branched product regioselective.
 5. Acatalyst in accordance with claim 4, wherein R¹ and R², alike ordifferent, are hydrogen or a carboxylato ester wherein the ester is analkyl or aryl group.
 6. A catalyst in accordance with claim 4, whereinR¹ and R², alike or different, are hydrogen or a carboxylato esterwherein the ester is an alkyl or aryl group.
 7. A catalyst in accordancewith claim 1, wherein said Y . . . Y group is --O(CH₂)_(y) O--,--(CH₂)_(y) --, --(C₆ H₄)--, --O(o--C₆ H₄)O-- or --O--Si--O--, in whichy is 2-5.
 8. A catalyst useful in the branched product regioselectivehydroformylation of olefins, having the formula: ##STR11## wherein R isany group which includes 2-5 carbon atoms directly within the1,3,2-dioxaphosphorus heterocyclic group and which does not interferewith the branched product regioselectivity of the catalyst as a whole,and Y . . . Y is --O(CH₂)_(y) O--, (CR⁴ R⁵)_(y) ⁻, --(C₆ H₄)--,--O(o--C₆ H₄)O-- or --O--Si--O--, in which y is 2-5, and R⁴ and R⁵ arehydrogen or any substituents which do not interfere with the ability ofthe final catalyst to the branched project regioselective, and L and L'are any ligand which complexes with the rhodium(I) atom in order tostabilize the molecule prior to use but which leaves the molecule insitu, and wherein the L and L' are both neutral, an anion is alsopresent.
 9. A catalyst in accordance with claim 8, wherein R is --(CR¹R²)_(x) -- in which x is 2-5, R¹ and R², alike or different, arehydrogen or any group which will not interfere with the ability of thecatalyst as a whole to be branched product regioselective, or a phenylgroup connected at ortho carbon atoms to the oxygen atoms of thedioxaphosphorus heterocycle, said phenyl group being unsubstituted orsubstituted by a substituent which will not interfere with the abilityof the catalyst as a whole to be branched product regioselective.
 10. Acatalyst in accordance with claim 9, wherein x is
 2. 11. A catalyst inaccordance with claim 9, wherein R¹ and R², alike or different, arehydrogen, lower alkyl, phenyl or a carboxylato ester, wherein the alkyl,phenyl or carboxylato ester groups are unsubstituted or substituted byany group which will not interfere with the ability of the catalyst as awhole to be branched product regioselective.
 12. A catalyst inaccordance with claim 11, wherein R¹ and R², alike or different, arehydrogen or a carboxylato ester wherein the ester is an alkyl or arylgroup.
 13. A catalyst in accordance with claim 8, wherein L and L' arean olefin, CO, a coordinating solvent, or both L groups combine into adiolefin, and said anion is also present.
 14. A catalyst in accordancewith claim 13, wherein said anion is BF₄ ⁻, PF₆ ⁻, ClO₄ ⁻ or a halide.15. A catalyst useful in the branched product regioselectivehydroformylation of olefins having the formula: ##STR12## wherein R isany group which includes 2-5 carbon atoms directly within the1,3,2-dioxaphosphorus heterocyclic group and which does not interferewith the branched product regioselectivity of the catalyst as a whole, Y. . . Y is any chain of 2-7 atoms which does not interfere with theability of the catalyst as a whole to be branched productregioselective, and L and L' are CO, a coordinating solvent, or both Lgroups combine into 1,5-cyclooctadiene, norbornadiene or1,3,5-hexadiene.
 16. A catalyst in accordance with claim 15, whereinsaid Y . . . Y group is --O(CH₂)_(y) O--, --(CH₂)_(y) --, --(C₆ H₄)--,--O(o--C₆ H₄)O-- or --O--Si--O--, in which y is 2-5.
 17. A catalyst inaccordance with claim 15, wherein R is --(CR¹ R²)_(x) -- in which x is2-5, R¹ and R², alike or different, are hydrogen or any group which willnot interfere with the ability of the catalyst as a whole to be branchedproduct regioselective, or a phenyl group connected at ortho carbonatoms to the oxygen atoms of the dioxaphosphorous heterocycle, saidphenyl group being unsubstituted or substituted by a substituent whichwill not interfere with the ability of the catalyst as a whole to bebranched product regioselective.
 18. A catalyst in accordance with claim17, wherein x is
 2. 19. A catalyst in accordance with claim 17, whereinR¹ and R², alike or different, are hydrogen, lower alkyl, phenyl or acarboxylato ester, wherein the alkyl, phenyl or carboxylato ester groupsare unsubstituted or substituted by any group which will not interferewith the ability of the catalyst as a whole to be branched productregioselective.
 20. A catalyst in accordance with claim 15, wherein saidY . . . Y group is --O(CH₂)_(y) O--, --(CH₂)_(y) --, --(C₆ H₄)--,--O(o--C₆ H₄)O-- or --O--Si--O--, in which y is 2-5.
 21. A catalystuseful in the branched product regioselective hydroformylation ofolefins, having the formula: ##STR13## wherein R is a phenyl groupconnected at ortho carbon atoms to the oxygen atoms of thedioxaphosphorus heterocycle, said phenyl group being unsubstituted orsubstituted by a substituent which does not interfere with the branchedproduct regioselectivity of the catalyst as a whole, and Y . . . Y isany chain of 2-7 atoms which does not interfere with the ability of thecatalyst as a whole to be branched product regioselective, said catalystbeing stabilized by coordination with one or more appropriate ligands.